Monoazo dyestuffs containing a 3, 6, 8-trisulfonaphthyl diazo component



United States Patent Office Patented Sept. 29, 1964 This inventionrelates to new azo dyestuffs. More particularly, the invention relatesto monoazo dyestuffs valuable as reactive dyestuffs for textilematerials containing acylatable hydroxyl and/ or amino groups, such asnatural and regenerated cellulose, wool, silk and superpolyamide fibres.

According to the invention there are provided the monoazo compounds ofthe formula:

wherein A stands for a trisulphonated naphthyl radical,

Y stands for a chlorine or hydrogen atom or an alkoxy or alkyl grouphaving 1 to 4 carbon atoms,

X stands for an aliphatic acyl group containing up to 5 carbon atoms,

R and R independently stand for a hydrogen atom or an alkyl group of 1to 4 carbon atoms, and

Z stands for an acyl radical which contains a reactive group, i.e, agroup capable of reaction with the fibre to form a covalent bond.

As examples of naphthyl radicals represented by A, there may bementioned, for example, 3,6,8-trisulpho-2- naphthyl,1,5,7-trisulpho-2-naphthyl, 1,3,7-trisulpho-2- naphthyl,2,4,6-trisulphol-naphthyl, 2,4,7-trisulpho-1- naphthyl, 2,5,7-trisulphol-naphthyl, 3,6,8-trisulpho-1- naphthyl and4,6,8-trisulpho-l-naphthyl.

As examples of aliphatic acyl groups represented by X, there may bementioned, for example, the radicals of aliphatic carboxylic andsulphonic acids, such as formic, acetic, butyric, methane-sulphonic andpropylsulphonic acids and radicals of carbamic acid containing up to 5carbon atoms such as carbamic, N-methyl carbamic and N,N-diethylcarbamicacids.

As examples of acyl radicals which are represented by Z there may bementioned, for example, the radicals of cup-unsaturated aliphaticcarboxylic acids such as acrylic acid, a-chloroacrylic acid, propiolicacid, maleic acid and monoand di-chloromaleic acids; more particularly,Z

may represent the radical of an acid which contains a labile halogenatom or a group which readily splits off to form an anion, for example,the radical of a halogenated aliphatic acid such as chloroacetic acid,fi-chloro and B- bromo-propionic acids and a,B-dichloropropionic acid ormore especially a heterocyclic radical which contains from 2 to 3nitrogen atoms in the heterocyclic ring and at least one halogen atom orother labile substituent on a carbon atom.

As examples of such heterocyclic radicals, there may be mentioned, forexample, s-triazines and pyrimidines which contain bromine, or,preferably, chlorine atoms, sulphonic acid groups, thiocyano groups,negatively substituted aryloxy and arylthiogroups, such assulphophenoxy, sulphophenylthio, nitrosulphophenoxy, disulphophenoxy andsulphonaphthoxy groups, or which contain groups of the formula:

-sc i I wherein Y represents the group of atoms necessary to form a 5-or 6-membered heterocyclic ring which may carry substituents or formpart of a fused ring system; or which contain quaternary ammonium orpyrimidinium groups; or which contain groups of the formula:

i f -SON R wherein R and R each represents the same or different alkyl,cycloalkyl, aryl or aralkyl groups, or R and R together form, togetherwith the nitrogen atom, a 5- or 6- membered heterocyclic ring; or whichcontain groups of the formula:

wherein R and R may be the same or difi'erent and each represents ahydrogen atom or an alkyl, aryl or aralkyl group.

In the cases where the pyrimidine ring or triazine ring carries only onelabile atom or group, the said ring may have one or more additionalsubstituents on the remaining carbon atoms. As examples of suchsubstituents, there may be mentioned, for example, cyano groups, aminoand substituted amino groups such as methylamino, ethylamino,dimethylamino, fl-hydroxyethylamino, di(,8- hydroxyethyl)amino,cyclohexylamino, phenylamino, sulphophenylamino, disulphophenylamino,carboxy sulphophenylamino, and carboxyphenylamino; alkoxy groups,preferably those containing from one to four carbon atoms; aryloxygroups, especially phenoxy, chlorophenoxy and methylphenoxy groups; andphenyl thio groups.

It is preferred that Z represents a triazine ring containing one or twochlorine atoms.

According to a further feature of the invention, there is provided aprocess for manufacture of the new azo dyestuffs which comprisesinteracting a monoazo compound of the formula:

wherein A, X, Y, R and R have the meanings stated above, with the acidhalide or anhydride of an acid which contains a group capable ofreaction with the fibre to form a covalent bond.

The treatment of the monoazo compound with the acid halide or anhydridemay conveniently be carried out by stirring an aqueous solution of thecompound with an aqueous suspension or solution of the acid halide oranhydride; the temperature of the reaction may vary from 0 to C.dependent on the ease with which water will react with the acid halideor anhydride group or the group capable of reacting with the fibre.

As examples of anhydrides or acid halides which may be used, there maybe mentioned for example, the anhydrides or acid halides of a;B-nnsaturated aliphatic acids such as chloromaleic anhydride, propiolylchloride and acrylyl chloride, the acid chlorides of halogenatedaliphatic acids such as chloroacetyl chloride, sulpho-chloroacetylchloride, B-bromo and chloropropionyl chloride and a-B-dichloropropionylchloride and preferably, heterchlorophenols, m and p-cresols, o, mandp-sulpho- V phenols, thiophenol, thioglycollic acid,dimethyldithiocarbamic acid, mercaptobezthiazole, methyl-, dimethyl-,ethyl, diethyl, n-propyl, iso-propyl-, butyl-, hexylor cyclohexyl-amine,toluidine, piperidine, morpholine, methoxyethylamine, ethanolamine,aminoacetic acid, aniline-2:5- disulphonic acid, orthanilic, metanilicand sulphanilic acids, 2-, 3- and 4-aminobenzoic acids,S-amino-Z-hydro-xybenzoic acid, Z-aminoethane-sulphonic acid,aminonaphthalene monoand di-sulphonic acids and N-methylamino ethanesulphonic acid.

The aminoazo compounds of Formula 5 may be obtained by diazotising atrisulphonated naphthylamine and coupling the diazonium compound soobtained with a compound of the formula:

NHR

As examples of trisulphonated naphthylamines which may be used for thispurpose, there may be mentioned, for example,2-naphthylamine-3,6,8-trisulphonic acid, 2- naphthylamine-l :5 :7-trisulphonic acid, 2-naphthylamine- 1,3,7-tnisulphonic acid,1-naphthylamine-2,4,6-trisulphonic acid,1-naphthylamine-2,4,7-trisulphonic acid,l-naphthylamine-2,5,7-trisulphonic acid, 1-naphthylamine-3,6,8-trisulphonic acid and 1-naphthylamine-4,6,8-trisulphonic acid.

As examples of compounds of Formula 6 which may be used for thispurpose, there may be mentioned, for example, m-aminoacetanilide,3-hydroxy-acetylaminoaniline, 2-methoxy-S-acetylaminoaniline,rn-ureidoaniline, 2- methyl-S-acetylaminoaniline, m-aminopropionanilide,3- methanesulphonylaminoaniline, 3 carbethoxyaminoaniline, and anilide.7

If desired, the new azo dyestuffs which contain, as the reactive group,a heterocyclic ring containing only a single chlorine or bromine atom,or one or two other labile groups on the heterocyclic ring may beobtained by taking one. of the new azo dyestuffs containing two chlorineor bromine atoms attached to the heterocyclic ring and replacing one orboth of these atoms by the appropriate group. This modified processforms a further feature of the invention. Thus, an amino or substitutedamino group may be introduced by reaction with ammonia or a primary orsecondary amine; an alkoxy or aryloxy (including negatively, substitutedaryloxy) group may be introduced by reaction with an alcohol, oraromatic hydroxyl compound; a sulphonic acid group may be introducedbyreaction with an alkali metal sulphite; a thiocyano group may beintroduced by reaction with potassium thiocyanate; a group of Formula 2above may be introduced by reaction with the alkali metal salt of amercaptoheterocyclic compound such as 2-mercaptobenzthiazole,2-mercaptobenzselcnazole, 2-mercaptobenziminazole, 2mercaptobenzoxazole, 2 mercaptopyridine, 2- mercapto 6methoxybenzthiazole, 2-mer'capt0-6-acetylaminobenzthiazole, Z-mercapto 6sulphobenzthiazole; a quaternary group may be introduced by treatmentwith pyridine or other tertiary amine; a group or" Formula 3 above maybe introduced by reaction with the appropriately substituted alkalidithiocarbamate such as sodium diethyl-dithiocalrbamate, sodiumdimethyldithiocarbamate, sodium diphenyl-dithiocarbamate and sodiumpentamethylenedithiocarbamate; and a group of Formula 4 above may beintroduced by reaction with a thio amide such as thio-acetamide andthioacetanilide.

The new monoazo dyestuffs are valuable for colouring cellulose textilematerials, for example, textile materials comprising natural orregenerated cotton. For colouring such textile materials, the new azodye stuffs are preferably applied, either by a dyeing or printingprocess, to the cellulose textile materials in conjunction with atreatment with an acid-binding agent, for example sodium hydroxide,sodium carbonate or sodium bicarbonate, which may be applied to thecellulose textile material before, during or after the application ofthe dyestuffs. When so applied to cellulose textile materials the newazo dyestuffs react with the cellulose and yield reddishyellow shadespossessing excellent fastness to light, to washing and to treatmentswith hypochlorite bleach. They are also distinguished by the low amountof staining caused by unreacted dyestuff on adjacent textile materialduring washing treatments after the colouration process.

The invention is illustrated but not limited by the following examplesin which parts are by weight:

Example I A solution of 4.1 parts of cyanuric chloride in 30 parts ofacetone is poured into a stirred mixture of 30 parts of crushed ice at03 C. A solution of 12.2 parts of trisodium 2-(2'-acetylamino 4aminophenylazo)naphthalene-3z6z8-trisulphonate in parts of water at pH7.0 is added and the mixture is stirred for 3 hours, 10 parts of 2 Nsodium carbonate solution being added to maintain the pH at 7 .0 and thetemperature being maintained at 0-3 C. by external cooling. Thesuspension is buffered at pH approm'mately 6.6 and 25 parts of sodiumchloride are added. The precipitated dyestutf' is filtered off, slurriedin acetone, refiltered and dried. Analysis shows the dyestuit containstwo hydrolysable chlorine atoms per molecule.

It yields bright reddish-yellow shades on cellulose materials whichpossess very good fastness to light an washing.

7 Example 2 parts of water is added at pH 7 .0. The mixture is stirredat 50 C. for 8-10 hours and cooled.

30 parts of sodium chloride are added and the precipitated dyestutf isfiltered oii, slurried in acetone, refiltered and dried at 40-50 C.Analysis shows the dyestulfi contains one hydrolysable chlorine atom permolecu e.

It yields bright reddish-yellow dyeings and prints on cellulosematerials possessing very good fastness'to light and to washing.

The same dyestufl may be obtained if, in Examplel, 10 parts of ammoniasolution of specific gravity 0.89 are added to the suspension ofdyestufi instead of adding butter and the mixture is stirred at 3540 C.for 3 hours.

Example 3 V p In Example 2 there is added a solution of 3.85 parts ofmetanilic acid in 30 parts of water, neutralised to pH 7.0 by addingsodium hydroxide solution, in place of ammonia. The condensation withthe aminoazo compound is carried out at 35-40 C. for 3 hours, parts of 2N sodium carbonate solution being added to maintain the pH at 7.0. Thesolution is cooled toroom temperature and parts of sodium chloridefollowed by 50 parts of anhydrous potassium acetate are added. Themixture is stirred for minutes and the precipitated dyestufi" isfiltered ofi, slurried in alcohol, refiltered and dried at C. Analysisshows that the dyestufi contains one atom of hydrolysable chlorine permolecule.

It yields bright reddish-yellow dyeings and prints possessing very goodfastness to light and washing.

ii filtered oflF, slurried in alcohol, refiltered and dried at 4050 C.Analysis shows that the dyestufr contains one atom of hydrolysablechlorine per molecule and is identical in properties with the dyestufiprepared as described in Example 3.

It yields bright reddish-yellow dyeings and prints possessing very goodfastness to light and washing.

The following table shows the results of condensation by the method ofExample 4 in which cyanuric chloride is condensed with the aminoazocompounds obtained from the components mentioned in columns I and II bycoupling, and the product condensed with the third components mentionedin column III. The shades of the resulting monochlorotriazine dyestuffsare given in column IV.

II III IV Example Diazo Component Coupling Component Third Component 52-naphtl1ylamine-3 zfiz8-trisulphonic acid 3-aminoacctanilideMcthylamine. Reddish-yellow. 6 do do Isobutylaminc D0. Taurine D0.Morpholineru Do. Do. Do. Do. Do. 3 :5 disulphoan' Do.4-sulphoanthranilic a Do. 5-sulphoanthranilio acid. Do. 3-sulphoN-methylanilinc Do. t-sulpho-N-methylanilinc Do. 2-mercaptobenzthiazole.Do. 4-sulphophenol Do. 6-sulpho-2-naphthol. Do. Potassium dithiocarbam.o. Do. Potassium diethyl dithio- Do.

carbamate. Z-naphthylamined :5 7-trisulphonic acid Do.2-napl1thylamine-l:3 7-trisulphonic acid Do. 1-naphtl1ylamine-2: 4:6-trisulphonic acid Do. 1-naphthylamine-2z4 7-trlsulphonic acid D0.1-naphthylamine-2z5 :7-trisulphonio acid D0. 1-naphthylamine-3 6;8-trisulphonic acid Do.

1-naphthyla1nine-4:6:S-trisulphonic acid- 3-carbOicyQ-naphthylamineGS-disulphonic acid. Z-naghthylamine-Elzfi:8-trisulphonic acid- 03-hydroxyacetylaminoanil B-amino-N-methyhnnfnnili do2-mtghoxy-5-acetylaminoauiline o Do. Reddislhyellow.

Golden yellow.

If in place of metanilic acid in this example there are used molecularequivalent amounts of aniline-3:5-disulphonic acid, sulphanilic acid,4-sulphoanthranilic acid or 5-sulphoanthranilic acid there are obtainedreddish-yellow dyestuifs having similar properties.

Example 4 A solution of 3.85 parts of metanilic acid in 30 parts ofWater is neutralised to pH 7.0 by adding sodium hydroxide solution andadded to. a suspension of the dyestuii prepared as described inExample 1. The mixture is stirred at 3540 C. for 3 hours, 10 parts of 2N sodium carbonate solution being added to maintain the pH at 7.0. Thesolution is cooled to room temperatureand 25 parts of sodium chloridefollowed by 50 parts. of anhydrous potassium acetate are added. Themixture is stirred for 30 minutes and the precipitated dyestufi is D Do.Do. Orange. Nmethylan.iline Do. 3-Sl1lDhn2T1ilinP D0.3:5-disulphoaniline Do. A mm nnia ReddiSh-YGHOW. 3-snlnhnanilinp Do.4-sulphoaniline Do. 3:5-disulphoanilide. Do. 5sulphoanthranilic acid Do.N-methylaniline D0. 3-sulpho-N-methylam'line- Do.-sulpho-N-methylaniline. Do.

Example 59 If in Example 1 there are used 12.5 parts of trisodium 2-(2'acetylarnino 4- N methylaminophenylazo)- naphthalene-3:628-trisulphonatein 156 parts of Water in place of the 12.2 parts of trisodium2-(2-acetylarnino-4- aminophenylazo)-naphthalene-3 16:8 trisulphonatethere is obtained a dyestufi which contains two hydrolysable atoms ofchlorine per molecule.

It yields bright reddish-yellow shades on cellulose materials whichpossess very good fastness to light and washmg.

Example 60 If in Example 1 there are used 7.0 parts of cyanuric bromidein place of the 4.1 parts of cyanuric chloride there is obtained asimilar dyestuff containing two hydrolysable atoms of bromine permolecule, which yields bright reddish-yellow dyeings and pirnts oncellulose materials which possess very good fastness to light andwasting. Example 61 A solution of 4.0 parts of2:4-dichloro-6-methoxy-striazine in 30 parts of acetone is poured into asolution of 12.2 parts of trisodium2-(2'-acetylamino-4-aminophenylazo)-naphthalene-316:8-trisulphonate in120 parts of water at pH 7.0. The mixture is stirred at 35-40 C. for 3hours, 10 parts of 2 N sodium carbonate solution being added to maintainthe pH at 7.0. The solution is cooled to room temperature and 20 partsof sodium chloride are added. The mixture is stirred to dissolve thesodium chloride and 200 parts of ethanol are added. The mixture isstirred for 30 minutes and the precipitated dyestuff is filtered off,slurried in acetone and dried at 4050 C. Analysis shows that thedyestutl contains one atom of hydrolysable chlorine per molecule.

It yields bright reddish yellow dyeings and prints possessing very goodfastness to light and washing.

Example 62 To a solution of 14.8 parts of themonochlorotriazinyldyestuil prepared as described in Example 2 in 150parts of water, there are added 40 parts of pyridine. The mixture isstirred at 85 C. for minutes, cooled to room temperature and poured into500 parts of acetone. The precipitated dyestuff is filtered oh and driedat 4050 C. Analysis shows the dyestufi contains no hydrolysable chlorineatoms per molecule.

It yields reddish-yellow shades on cellulose materials 1 which possessvery good fastness to light and washing.

Example 63 To a solution of 18.3 parts of the monochlorotriazinyldyestutf prepared as described in Example 3 in 150 parts of water thereare added 40 parts of pyridine. The mixture is stirred at 85 C. for 15minutes, cooled to room temperature and poured into 600 parts ofacetone. The precipitated dyestuii is filtered oil and dried at 40-50 C.Analysis shows the dyestuif contains no hydrolysable atoms of chlorineper molecule.

It yields reddish-yellow shades on cellulose materials which possessvery good fastness to light and washing.

' Example 64 materials which possess very good .fas'tness to light andwashing.

Example 66 12.2 parts of trisodium2-(2'-acetylamino-4-aminophenylaZo)naphthalene-3:6:8-trisulphonate aredissolved in 120 parts of water and to. the solution is added a solutionof 4.6 parts of S-cyano-Zz4z6-trichloropyrimidine in 30 parts ofacetone. The mixture is stirred at C. for four hours, 9 parts of 2 Nsodium-carbonate solution being added to maintain the pH at 7.0. Themixture is cooled, filtered and poured into 1000 parts of acetone. Theprecipitated dyestufl is filtered off and dried at 40- 50 C. Analysisshows that the dyestufi contains two hydrolysable chlorine atoms permolecule.

It yields reddish-yellow dyeings and prints on cellulose materials whichpossess very good fastness to light and washing.

Example 67 If in Example 66 there is used in equivalent quantity oftrichloropyrimidine in place of 5-cyano-2:4:6-trichloropyrimidine thereis obtained a dyestuff which yields bright reddish-yellowdyeings andprints on cellulose materials which possess very good fastness to lightand washing.

Example 68 9 parts of acrylyl chloride dissolved in 20 parts of acetoneare cautiously added to a neutral solution of 12.2 parts of2-(2-acetylamino-4'-aminophenylazo)naphthalene-3:6:8-trisulphonate in120 parts of water at 0 C. The solution is allowed to warm up to roomtemperature and is stirred for 20 hours, 2 N sodium carbonate solutionbeing added to maintain the pH at 7.0. When the condensation is complete20 parts of sodium chloride are added and the precipitated dyestuff isfiltered oflt', slurn'ed in acetone and dried at 4050 C.

It yields reddish-yellow shades on cellulose materials which possessvery good fastness to light and washing.

Example 69 7 obtained a dyestuif which yields reddish-yellow shades oncellulose materials possessing very good fastness to light and washing.

To a solution of 15.2 parts of the dichlorotriazinyl dyestuff, preparedas described in Example 1, in 150 parts of water at pH 7.0 there areadded 12 parts of 40% sodium bisulphite solution and 5.4 parts of 32%sodium hydroxide solution. The solution is stirred at room temperaturefor 18 hours.

Example 65 To a solution of 12.2 parts of trisodium2-(2-acetylamino-4-aminophenylazo)naphthalene-3:6z8 trisulphonate in 120parts of water is added a solution of 4.8 parts of tetrachloropyrimidinein 150 parts of dioxan. The mixture is stirred under reflux for 48 hoursat 90 C., 2 N sodium carbonate solution being added. to maintain thepl-I at 7.0. When the reaction is complete the mixture is evaporated toone half of the original volume and 15 parts of sodium chloride added.The precipitated dyestuif is filtered oil and dried at 40-50 C.

It yields reddish-yellow dyeings and prints on cellulose The solution isbuffered at pH 6.6 by adding 5 parts of a mixture of 1 part ofsodium'bisul- Example 70 If in Example 68 there are used 14 parts of'a-ChIOI'O- acetyl chloride in place of the acrylyl chloride there isobtained a dyestutf which yields reddish-yellow shades on cellulosematerials possessing very good fastnessto light and washing.

What we claim is:

Y stands for a member selected from the group consisting of hydrogen,lower alkyl, and lower alkoxy;

X stands for a saturated aliphatic acyl group containing from 1 to 5carbon atoms;

R stands for a member selected from the group consisting of hydrogen andmethylgand Z is a reactive radical selected from the class consisting ofacyl radicals of mil-unsaturated lower aliphatic carboxylic acids, acylradicals of chloro-substituted lower aliphatic acids,dibromo-s-triazinyl, dichloro-s-triazinyl, radicals of the formula:

II -C1 -o l in which X is selected from H, Cl and CN, radicals of theformula:

in which X is selected from the class consisting of Cl,

NH sulphoanilino, disulphoanilino, sulphocarboxyanilino, loweralkylamino, B-sulphoethylamino, morpholino, B-hydroxyethylaznino,anilino, N-n1ethylanilino, N methylsulphoanilino, benzthiazol 2- ylthio,sulphophenoxy, sulphonaphthoxy, dithiocarbamyl, di(l0wer alkyl)thiocarbamyl and lower alkoxy, and radicals of the formula:

10 in which X is selected from the class consisting of amino andsulphanilino.

31 so H N=N-NHO CNH;

] HO S S0 11 NHCONH:

([31 so H C\ a fi \DII -N=N-NHC 0-01 1 N HO S- S0 11 NHCOCH ReferencesCited in the file of this patent UNITED STATES PATENTS 2,903,442 Ria-tSept. 8, 1959 2,945,022 Fasciati et a1 July 12, 1960 2,951,071 TilleyAug. 30, 1960 2,951,072 Tilley et a1 Aug. 30, 1960 2,951,836 StephenSept. 6, 1960 2,951,837 Andrew et a1 Sept. 6, 1960 3,040,024 Riat et alJune 19, 1962 FOREIGN PATENTS 224,012 Australia Dec. 1, 1960

1. A COMPOUND OF THE FORMULA: